U.S. patent number 10,465,039 [Application Number 15/596,996] was granted by the patent office on 2019-11-05 for epoxy curing agents, compositions and uses thereof.
This patent grant is currently assigned to Evonik Degussa GmbH. The grantee listed for this patent is EVONIK DEGUSSA GMBH. Invention is credited to Sudhir Ananthachar, Nergiz Bozok, Shafiq Fazel, Michael Oberlander, Robert Rasing, Shiying Zheng.
United States Patent |
10,465,039 |
Zheng , et al. |
November 5, 2019 |
Epoxy curing agents, compositions and uses thereof
Abstract
The present invention relates to epoxy curing agents which are
obtained from the reaction of a polyalkylene polyether modified
polyepoxide resin and a polyamine component. They polyamine
component is a reaction product of a polyethylene polyamine having
3 to 10 nitrogen atoms, for example, diethylenetriamine (DETA), and
at least one aldehyde having 1 to 8 carbon atoms, for example,
formaldehyde. The epoxy curing agent may be used as part of a two
component coating system in the curing of liquid or pre-dispersed
curable epoxy resins.
Inventors: |
Zheng; Shiying (Center Valley,
PA), Ananthachar; Sudhir (Hillsborough, NJ), Rasing;
Robert (Rotterdam, NL), Bozok; Nergiz (Utrecht,
NL), Fazel; Shafiq (Allentown, PA), Oberlander;
Michael (Topton, PA) |
Applicant: |
Name |
City |
State |
Country |
Type |
EVONIK DEGUSSA GMBH |
Essen |
N/A |
DE |
|
|
Assignee: |
Evonik Degussa GmbH (Essen,
DE)
|
Family
ID: |
59679339 |
Appl.
No.: |
15/596,996 |
Filed: |
May 16, 2017 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20170247501 A1 |
Aug 31, 2017 |
|
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
15343632 |
Nov 4, 2016 |
|
|
|
|
62256262 |
Nov 17, 2015 |
|
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07D
233/02 (20130101); C08G 59/245 (20130101); C09D
163/00 (20130101); C04B 28/04 (20130101); C08G
59/502 (20130101); C08G 59/56 (20130101); C08G
59/60 (20130101); C07D 487/08 (20130101); C08G
59/5073 (20130101); C08G 59/508 (20130101); C04B
24/281 (20130101); C04B 2201/52 (20130101) |
Current International
Class: |
C08G
59/50 (20060101); C08G 59/24 (20060101); C07D
487/08 (20060101); C04B 28/04 (20060101); C09D
163/00 (20060101); C04B 24/28 (20060101); C08G
59/56 (20060101); C08G 59/60 (20060101); C07D
233/02 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
103333136 |
|
Oct 2013 |
|
CN |
|
2321509 |
|
Nov 1973 |
|
DE |
|
0458502 |
|
Nov 1991 |
|
EP |
|
H06122754 |
|
May 1994 |
|
JP |
|
5408612 |
|
Feb 2014 |
|
JP |
|
2013003202 |
|
Jan 2013 |
|
WO |
|
Other References
Araki Macromol. vol. 21, No. 7, 1997-2001. cited by examiner .
Araki et al.; Macromolecules: Site-Selective Derivatization of
Oligoethylenimines Using Five-Membered-Ring Protection Method, vol.
21, No. 7, 1988, pp. 1995-2001, XP055346775 (8 pages). cited by
applicant .
van Alphen, J. et al; N.N'-Di-(Benzyl)-Ethylenediamine:(Alkylated
Ethylenediamnine derivates I); vol. 54, No. 2, pp. 93-96,
XP055346671 (4 pages). cited by applicant .
Hine, J. et al; Imines, Imidazolidines, and Imidazolidinium Ions
from the Reactions of Ethylenediamine Derivates with
Isobutyraldehyde and Acetone; Journal of American Cancer Society;
1973, Columbus, Ohio, XP055346492 (7 pages). cited by applicant
.
Tanaka; Synthesis and Characteristics of Epoxides, C.A. May, ed;
Epoxy Resins Chemistry and Technology; Marcel Dekker; 1988; (11
pages). cited by applicant .
Huntsman; Ethyleneamines: A Global Profile of Products and
Services; 2007; (76 pages). cited by applicant .
Gajendra D. Khune and Nanasaheb G. Ghatge; Amine Aldehyde
Condensation Products for Stabilization of Natural Rubber Latex
Foam; Journal of Macromolecular Science; Part A--Chemistry; Pure
and Applied Chemistry, col. A(15), No. 1, pp. 153-168; 1981. (16
pages). cited by applicant .
Ukrainskii Khimicheskii Zhumal (Russian Edition), vol. 54, Issue 4,
p. 387-389, Journal, 1988. (3 pages). cited by applicant .
H. Lee and K. Neville; Handbook of Epoxy Resins; Chapter 5:
Epoxy-Resin Curing Mechanisms; McGraw Hill; New York; 1967; pp. 5-1
to 5-25 (13 pages). cited by applicant.
|
Primary Examiner: Butcher; Robert T
Attorney, Agent or Firm: Chung; Andrew H. Li; Linda S. Ngui;
Jason S.
Claims
The invention claimed is:
1. A curing agent composition comprising the reaction product of:
(a) a polyamine comprising at least one saturated heterocyclic
compound having two nitrogen heteroatoms according to formula (II)
##STR00006## wherein X is selected from a hydrogen atom, a linear
or branched C.sub.1 to C.sub.4 alkyl group and a substituted or
unsubstituted phenyl group, Y.sub.1 is a direct bond or a divalent
polyethylene polyamine group having 1 to 8 nitrogen atoms, and R is
independently a hydrogen atom or a group selected from
C.sub.1-C.sub.8 linear, cyclic, and branched alkyl, alkenyl, and
alkaryl groups; and (b) a polyalkylene polyether modified
polyepoxide resin.
2. The curing agent composition of claim 1 further comprises at
least one multifunctional amine having 2 or more active amine
hydrogens.
3. The curing agent composition of claim 2 further comprises
water.
4. The curing agent composition of claim 2, wherein the at least
one multifunctional amine is an aliphatic amine, a cycloaliphatic
amine, an aromatic amine, a Mannich base derivative of an aliphatic
amine, a cycloaliphatic amine, or an aromatic amine, a polyamide
derivative of an aliphatic amine, a cycloaliphatic amine, or an
aromatic amine, an amidoamine derivative of an aliphatic amine, a
cycloaliphatic amine, or an aromatic amine, an amine adduct
derivative of an aliphatic amine, a cycloaliphatic amine, or an
aromatic amine, or any combination thereof.
5. The curing agent composition of claim 1, wherein X is hydrogen
and R is hydrogen.
6. The curing agent composition of claim 1, wherein the
polyalkylene polyether modified polyepoxide resin comprises the
reaction product of: a polyalkylene polyether polyol and a
polyepoxide compound.
7. The curing agent composition of claim 6 wherein the polyalkylene
polyether polyol comprises polyethylene glycol.
8. The curing agent composition of claim 1, wherein the
polyalkylene polyether modified polyepoxide resin comprises the
reaction product of: a polyepoxide compound and a
polyetheramine.
9. The curing agent composition of claim 1, further comprises
water.
10. The curing agent composition of claim 1, further comprises
isophorone diamine.
11. The curing agent composition of claim 1, further comprises a
co-curing agent selected from an amidoamine curing agent, an
aliphatic curing agent, a polyamide curing agent, a cycloaliphatic
curing agent, or a Mannich base curing agent.
12. An amine-epoxy composition comprising: the reaction product of
a curing agent and an epoxy composition, wherein the epoxy
composition comprises at least one multifunctional epoxy resin, and
wherein the curing agent comprises: a reaction product of at least
one polyamine and at least one polyalkylene polyether modified
polyepoxide resin, wherein the at least one polyamine comprises at
least one saturated heterocyclic compound having two nitrogen
heteroatoms according to formula (II) ##STR00007## wherein X is
selected from a hydrogen atom, a linear or branched C.sub.1 to
C.sub.4 alkyl group and a substituted or unsubstituted phenyl group
Y.sub.1 is a direct bond or a divalent polyethylene polyamine group
having 1 to 8 nitrogen atoms, and R is independently a hydrogen
atom or a group selected from C.sub.1-C.sub.8 linear, cyclic, and
branched alkyl, alkenyl and alkaryl groups.
13. The composition of claim 12, wherein the composition further
comprises water.
14. An article of manufacture comprising the composition of claim
12.
15. The article of claim 14, wherein the article is an adhesive, a
coating, a primer, a sealant, a curing compound, a construction
product, a flooring product, or a composite product.
16. A process for the preparation of a curing agent for aqueous
epoxy resin compositions, comprising: (a) reacting a polyethylene
polyamine having 3 to 10 nitrogen atoms with at least one aldehyde
having 1 to 8 carbon atoms to produce a polyethylene polyamine
component, wherein the polyethylene polyamine component comprises
at least one saturated heterocyclic compound having two nitrogen
heteroatoms according to formula (II) ##STR00008## wherein X is
selected from a hydrogen atom, a linear or branched C.sub.1 to
C.sub.4 alkyl group and a substituted or un-substituted phenyl
group, Y.sub.1 is a direct bond or a divalent polyethylene
polyamine group having 1 to 8 nitrogen atoms, and R is
independently a hydrogen atom or a group selected from
C.sub.1-C.sub.8 linear, cyclic, and branched alkyl, alkenyl, and
alkaryl group; and (b) reacting the polyethylene polyamine
component with at least one polyalkylene polyether modified
polyepoxide resin to produce a curing agent.
17. The process of claim 16, further comprising (c) mixing the
curing agent with water.
18. An epoxy modified cement composition comprising: (A) an epoxy
composition comprising at least one multifunctional epoxy resin
having at least two epoxide groups per molecule; (B) a curing agent
comprising water and the reaction product of: (1) a polyalkylene
polyether modified polyepoxide resin component, and (2) a polyamine
component comprising at least one saturated heterocyclic compound
having two nitrogen heteroatoms according to formula (II)
##STR00009## wherein X is selected from a hydrogen atom, a linear
or branched C.sub.1 to C.sub.4 alkyl group and a substituted or
unsubstituted phenyl group, Y.sub.1 is a direct bond or a divalent
polyethylene polyamine group having 1 to 8 nitrogen atoms, and R is
independently a hydrogen atom or a group selected from
C.sub.1-C.sub.8 linear, cyclic, and branched alkyl alkenyl, and
alkaryl groups; and (C) a solid component comprising at least one
hydraulic inorganic binder.
Description
FIELD OF THE INVENTION
The present invention relates generally to curing agents for epoxy
resin, the amine-epoxy compositions derived therefrom and articles
produced from such compositions. Methods for making and using the
curing agents and compositions are also disclosed.
BACKGROUND OF THE INVENTION
Epoxy resin based systems are widely used as sealing materials,
coating compositions, adhesives, and the like, in a variety of
fields such as electricity, electronics, and civil engineering and
construction. When cured, they exhibit excellent electrical
insulating properties, are moisture proof, heat resistant,
soldering resistant, chemical resistant, durable, have excellent
adhesive properties and mechanical strength. Specific examples
include epoxy composite materials using carbon fiber and fiberglass
reinforcements, protective coatings for metal surfaces, and
protective coatings for concrete, cementitious or ceramic
substrates, often referred to as civil engineering
applications.
Two part epoxy resin based systems generally include a curable
epoxy resin and a curing agent for the epoxy resin. The two
components chemically react with each other to form a cured epoxy,
which is a hard, duroplastic material. Epoxy resins are substances
or mixtures which contain epoxide groups. The curing agents include
compounds which are reactive to the epoxide groups of the epoxy
resins, such as amines, carboxylic acid, and mercaptanes.
During preparation, one or both of the epoxy resin and curing agent
are dispersed or dissolved in a solvent, for example, an organic
solvent, to reduce viscosity. Significant environmental and safety
concerns are created due to the use of such solvent-based systems
since the associated volatile organic compounds (VOCs) create
environmental pollution and health hazards.
A variety of epoxy resin curing agents dissolved or emulsified in
water have been developed to address the environmental and health
concerns. For example: U.S. Pat. No. 4,197,389 discloses a curing
agent prepared by reacting at least one polyepoxide compound with
at least one polyalkylene polyether polyol to form an adduct which
is subsequently reacted with a polyamine; U.S. Pat. No. 5,032,629
describes water compatible polyamine-epoxy adducts prepared by
reacting poly(alkylene oxide) mono- or diamines with a polyepoxide
to form intermediates which are then subsequently reacted with an
excess of a polyamine; U.S. Pat. No. 6,245,835 describes
amino-epoxy adduct curing agents prepared by reacting a
polyoxyalkylenediamine with a polyepoxide and polyoxyalkylene
glycol diglycidyl ether and emulsifying the reaction product in
water.
Many current waterborne curing agent and epoxy systems are plagued
with problems which limit their usefulness. One problem is cured
coatings having poor physical properties, such as hardness,
appearance and solvent resistance. Other problems are a relatively
high viscosity of the curing agent, making the coatings difficult
to apply. Additional problems include a slow cure speed, short pot
life and manufacturing difficulties. It is an object of the present
invention to provide a novel, low VOC, waterborne curing agent for
use with epoxy resin compositions, which overcomes these problems.
It is also an object of the present invention to provide waterborne
curing agents that, can be easily manufactured, have improved pot
life and exhibit low viscosity, even at high solids content.
SUMMARY OF THE INVENTION
In one aspect, the present invention provides an epoxy curing agent
for a curable epoxy resin. The curing agent comprises the reaction
product of a polyalkylene polyether modified polyepoxide resin
component and a polyamine component which is the reaction product
of a polyethylene polyamine and an aldehyde. In a preferred
embodiment, the polyamine component is the reaction product of
diethylenetriamine (DETA) and formaldehyde. The curing agent
comprises the contact product of the curing agent described above
and water.
In another aspect, the present invention provides a method for the
preparation of the epoxy curing agent such that the reaction
product contains active amine hydrogens capable of reacting with a
curable epoxy resin.
In still another aspect, the present invention relates to the use
of the above curing agent for curing a liquid or pre-dispersed
epoxy resin in a two component amine-epoxy system. The amine-epoxy
systems comprising the epoxy curing agent of the present invention
have a fast cure rate, and a cured composition which exhibits good
chemical resistance, fast hardness development, good gloss and
stability. Articles of manufacture produced from amine-epoxy
compositions disclosed herein include, but are not limited to,
adhesives, coatings, primers, sealants, curing compounds,
construction products, flooring products, and composite
products.
DETAILED DESCRIPTION
The ensuing detailed description provides preferred exemplary
embodiments only, and is not intended to limit the scope,
applicability, or configuration of the invention. Rather, the
ensuing detailed description of the preferred exemplary embodiments
will provide those skilled in the art with an enabling description
for implementing the preferred exemplary embodiments of the
invention. Various changes may be made in the function and
arrangement of elements without departing from the spirit and scope
of the invention, as set forth in the appended claims.
In the claims, letters may be used to identify claimed method steps
(e.g. a, b, and c). These letters are used to aid in referring to
the method steps and are not intended to indicate the order in
which claimed steps are performed, unless and only to the extent
that such order is specifically recited in the claims.
Contact product, as used herein, describes a composition wherein
the components are contacted together in any order, in any manner,
and for any length of time, including the possibility that two or
more of the components may react with one another forming other
components. For example, the components can be contacted by
blending or mixing. Further, contacting of any component can occur
in the presence or absence of any other component of the
compositions or formulations described herein. Combining additional
materials or components can be done by any method known to one of
skill in the art. Further, the term "contact product" includes
mixtures, blends, solutions, dispersions, slurries, reaction
products, and the like, or combinations thereof. Although "contact
product" can include reaction products, it is not required for the
respective components to react with one another.
Reaction product, as used herein, describes a composition wherein
one or more of the components are produced as a result of a
chemical reaction between two or more reactants.
As used herein, pot life in coating application refers to the time
period in which a composition is sufficiently liquid such that it
may be applied to a substrate material, and achieve desired quality
coatings.
The phrases "in one embodiment," "according to one embodiment," and
the like generally mean the particular feature, structure, or
characteristic following the phrase is included in at least one
embodiment of the present invention, and may be included in more
than one embodiment of the present invention. Importantly, such
phrases do not necessarily refer to the same embodiment.
The present invention is generally directed to epoxy curing agents
and methods of making and using such epoxy curing agents. These
waterborne epoxy curing agents can be used to cure, harden and/or
cross-link a curable epoxy resin.
The curing agents of the present invention are simple to
manufacture and deliver a fast cure speed when used to cure liquid
epoxy resin and solid epoxy resin dispersions. The coating
compositions prepared with the curing agents described herein have
a relatively low viscosity, making them easy to apply to
substrates, and an acceptable pot life. The cured coating
compositions exhibit fast hardness development and good film
appearance.
An aspect of the present invention is a curing agent comprising the
reaction product of: (1) a polyalkylene polyether modified
polyepoxide resin component, and (2) a polyamine component, which
is the reaction product of (2a) a polyethylene polyamine and (2b)
an aldehyde. In a preferred embodiment, the polyamine component is
the reaction product of DETA and formaldehyde.
Aqueous or waterborne curing agent compositions are within the
scope of the present invention. Waterborne curing agent
compositions comprise the contact product of the above described
curing agent and water. Such aqueous curing agent compositions
preferably comprise 30 to 80 wt % solids, more preferably 50 to 70
wt % solids.
Generally, the curing agent compositions have an amine hydrogen
equivalent weight (AHEW) based on 100% solids from about 30 to
about 500. Further, such curing agent compositions can have an AHEW
based on 100% solids in the range from about 50 to about 450, from
about 50 to about 400, from about 50 to about 350, from about 50 to
about 300, from about 50 to about 250, from about 50 to about 200,
from about 100 to about 250, or from about 100 to about 200.
The curing agent compositions may be used as one component of a
two-component amine-epoxy coating composition, wherein the second
component is a curable epoxy component. The epoxy component of the
two component coating composition comprises an epoxy resin or an
epoxy resin dispersion.
(1) The Polyalkylene Polyether Modified Polyepoxide Resin Component
of the Curing Agent
The polyalkylene polyether modified polyepoxide resin may be
produced by any effective method, for example, by reacting a
polyepoxide compound with a polyalkylene polyether polyol, or by
reacting a polyepoxide compound with a polyetheramine.
In an embodiment, the modified polyepoxide resin component is
prepared via a polyalkylene polyether polyol. Polyalkylene
polyether modified polyepoxide resins useful in the current
invention may comprise the reaction product of: (i) at least one
polyepoxide compound and (ii) at least one polyalkylene polyether
polyol. Suitable polyepoxide compounds and admixtures thereof are
disclosed in U.S. Pat. No. 4,197,389. The disclosure of U.S. Pat.
No. 4,197,389 is incorporated herein by reference in its
entirety.
The at least one polyepoxide compound includes, but is not limited
to, a diglycidyl ether of bisphenol A, a diglycidyl ether of
bisphenol F, an epichlorohydrin-derived compound, or a combination
thereof. Generally, polyepoxide resins with epoxy equivalent
weights in the range from about 160 to about 2000 are useful in the
present invention. In a preferred embodiment, the at least one
polyepoxide resin comprises a difunctional bisphenol
A/epichlorohydrin-derived liquid epoxy resin.
Suitable polyalkylene polyether polyols are described in U.S. Pat.
No. 4,197,389. Non-limiting examples of polyalkylene polyether
polyols that are useful in the present invention include, but are
not limited to, polyethylene glycols, polypropylene glycols, or
combinations thereof. Mixtures of different molecular weight
polyalkylene polyether polyols can be used, as well as mixtures of
different polyalkylene polyether polyols. The combinations of the
different polyether polyols can be mixed first and then reacted
with the polyepoxide resin, or can be reacted separately with the
polyepoxide resin and subsequently mixed or blended. Generally,
polyalkylene polyether polyols with number average molecular
weights in the range from about 200 to 10,000, from about 400 to
about 8000, from about 600 to about 5000, or from about 800 to
about 2500, are useful in the present invention.
The polyepoxide resin can be reacted with the polyalkylene
polyether polyol in accordance with the process described in U.S.
Pat. No. 4,197,389. Often, a Lewis acid catalyst is used to promote
the reaction, such as a BF.sub.3-amine complex which is a
well-known catalyst to those of skill in the art. In addition, the
reaction can be conducted in the presence of monoepoxides and
solvents or softeners, as is known to those of skill in the art.
Exemplary monoepoxides that can be used in admixture with the
polyepoxide resin include, but are not limited to, epoxidized
unsaturated hydrocarbons such as butylene, cyclohexene, and styrene
oxides, and the like; halogen-containing epoxides such as
epichlorohydrin; epoxyethers of monohydric alcohols such as methyl,
ethyl, butyl, 2-ethylhexyl, dodecyl alcohol, and the like;
epoxy-ethers of monohydric phenols such as phenol, cresol, and
other phenols substituted in the ortho or para positions; glycidyl
esters of unsaturated carboxylic acids; epoxidized esters of
unsaturated alcohols or unsaturated carboxylic acids; acetals of
glycidaldehyde; or combination thereof.
To produce polyalkylene polyether modified polyepoxide resins
useful in the present invention, the reactant ratio of epoxy groups
in the polyepoxide compound to the hydroxyl groups in the
polyalkylene polyether polyol is generally within a range from
about 1.5:1 to about 8:1. The reactant ratio, in accordance with
another aspect of the present invention, is about 1.6:1, about 2:1,
about 2.5:1, about 3:1, about 3.5:1, about 4:1, about 4.5:1, about
5:1, about 5.5:1, about 6:1, about 6.5:1, about 7:1, or about
7.5:1. In yet another aspect, the reactant ratio is in a range from
about 1.8:1 to about 6:1. In a further aspect, the reactant ratio
of epoxy groups in the polyepoxide compound to the hydroxyl groups
in the polyalkylene polyether polyol is in a range from about 2:1
to about 4:1.
In an embodiment, the polyalkylene polyether modified polyepoxide
resin component is prepared via the reaction of amino-terminated
polyalkylene polyether (polyetheramine) with a polyepoxide
compound. Polyalkylene polyether modified polyepoxide resins useful
in the current invention comprise the reaction product of: (i) at
least one polyepoxide compound and (ii) at least one
polyetheramine.
Polyetheramines useful for reacting with the polyepoxide resin
component include compounds which contain primary amino groups
attached to the end of a polyether backbone. The polyether backbone
is normally based on either propylene oxide (PO), ethylene oxide
(EO), or mixed PO/EO. Preferably the polyether amine is a monoamine
having an average molecular weight from about 500 to about 4000, or
about 500 to about 3,000, or about 500 to about 2,000. The reaction
product of a polyether amine and a polyepoxide compound is
disclosed in U.S. Pat. No. 5,489,630 and is incorporated herein by
reference in its entirety. The ratio of epoxide groups in the
polyepoxide compound to active amine hydrogen atoms in
polyetheramine is about 1.1:1 to 6:1.
Specific examples of polyetheramines are Jeffamine.RTM. M-600,
Jeffamine.RTM. M-1000, Jeffamine.RTM. M-2005, Jeffamine.RTM. M-2070
amines, Jeffamine.RTM. D-2000, Jeffamine.RTM. ED-600,
Jeffamine.RTM. ED-900, and Jeffamine.RTM. ED-2001 amines. The
Jeffamine.RTM. materials are commercially available from the
Huntsman Corp. The preferred polyetheramine is Jeffamine.RTM.
M-1000 amine which is a monoamine terminated block copolymer of
propylene oxide and ethylene oxide.
The reaction to produce the polyalkylene polyether modified
polyepoxide resin is carried out by adding the polyetheramine to
the polyepoxide resin component at a temperature range of 50
degrees C. to 120 degrees C. The addition is performed at a
controlled rate to minimize the temperature increase created by the
exothermic reaction.
(2) The Polyamine Component of the Curing Agent
In an embodiment, the polyamine component of the curing agent (2)
is the reaction product of (2a) a polyethylene polyamine having 3
to 10 nitrogen atoms and (2b) a C.sub.1 to C.sub.8 aldehyde.
The polyethylene polyamine compounds having 3 to 10 nitrogen atoms
(2a) that are useful in producing the curing agent polyamine
component include a polyethylene polyamine according to formula
(I):
##STR00001## wherein R is independently a hydrogen atom or a group
selected from C.sub.1-C.sub.8 linear, cyclic, and branched alkyl,
alkenyl, and alkaryl groups; n is an integer from 1 to 8. Suitable
examples of R include hydrogen atom, methyl, isopropyl, and benzyl
group. Suitable polyethylene polyamine compounds having 3 to 10
nitrogen atoms according to the present disclosure include, but are
not limited to, diethylenetriamine (DETA), triethylenetetramine
(TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine
(PEHA), and mixtures thereof. Preferable examples of the
polyethylene polyamine compounds having 3 to 10 nitrogen atoms
include DETA, TETA, and TEPA, more preferably TETA and DETA, and
most preferably DETA.
The polyethylene polyamine compounds having 3 to 10 nitrogen atoms
can be used individually or mixed with one another. It is to be
understood that commonly available polyethylene polyamine compounds
having 3 to 10 nitrogen atoms such as TETA, TEPA, and PEHA are
mixtures of linear and branched isomers and other congeners having
cyclic structures. Some of the linear and branched isomers are
shown above. These commonly available polyethylene polyamine
compounds are included in the definition of polyethylene polyamine
compounds of the present disclosure.
The polyethylene polyamine compounds having 3 to 10 nitrogen atoms
can be substituted with alkyl groups. Examples include alkylated
polyethylene polyamine as disclosed in U.S. Pat. No. 8,518,547 and
benzylated polyethylene polyamine as disclosed in U.S. Pat. Nos.
8,147,964 and 8,168,296. The above referenced patents are hereby
incorporated by reference.
The C.sub.1 to C.sub.8 aldehyde compounds (2b) that are useful in
producing the curing agent polyamine component include but are not
limited to, formaldehyde, acetaldehyde, propionaldehyde,
butyraldehyde, isobutyraldehyde, trimethylacetaldehyde,
2-methylbutyraldehyde, isovaleraldehyde, valeraldehyde, hexanal,
phenylacetaldehyde, benzaldehyde, vanillic aldehyde (also known as
vanilline), o-tolualdehyde, o-anisaldehyde, salicylaldehyde, and
4-hydroxylbenzaldehyde. Preferable C.sub.1 to C.sub.8 aldehyde
compounds include formaldehyde, acetaldehyde, benzaldehyde,
tolualdehyde, o-anisaldehyde, and salicylaldehyde. More preferable
C.sub.1 to C.sub.8 aldehyde compounds include formaldehyde, and
benzaldehyde, and most preferable is formaldehyde. When
formaldehyde is used as the C.sub.1 to C.sub.8 aldehyde compound,
it is typically used as an aqueous solution with some methanol as
stabilizer for easy handling. For easy handling, the trimer of
formaldehyde, 1,3,5-trioxane, and the oligomer and polymer form,
paraformaldehyde are used as equivalent to formaldehyde aqueous
solution since both are solid. In the present disclosure,
paraformaldehyde is used as equivalent to formaldehyde.
The polyethylene polyamine having 3 to 10 nitrogen atoms (2a) and
the C.sub.1 to C.sub.8 aldehyde (2b) are reacted according to
methods and conditions discussed below to form a reaction product
which is the polyamine component (2) of the curing agent. In an
embodiment, the reaction product of the polyethylene polyamine
having 3 to 10 nitrogen atoms and the C.sub.1 to C.sub.8 aldehyde
comprises at least one saturated heterocyclic compound having two
nitrogen heteroatoms according to formula (II), below.
##STR00002## wherein X is independently selected from a hydrogen
atom, a linear or branched C.sub.1 to C.sub.4 alkyl group and a
substituted or un-substituted phenyl group, Y.sub.1 is a direct
bond or a divalent polyethylene polyamine group having 1 to 8
nitrogen atoms or a divalent polyethylene polyamine derivative
having 1 to 8 nitrogen atoms, and R is independently a hydrogen
atom or a group selected from C.sub.1-C.sub.8 linear, cyclic, and
branched alkyl, alkenyl, and alkaryl groups. The C.sub.1 to C.sub.4
alkyl groups and the polyethylene polyamine groups having 1 to 8
nitrogen atoms may be branched or unbranched.
Preferable examples for X include hydrogen atom, methyl, ethyl,
isopropyl, n-propyl, phenyl, iso-butyl, and n-butyl group. More
preferable examples of X include hydrogen atom, methyl, and phenyl
group. A most preferable example of X is hydrogen atom. Preferable
examples of R include hydrogen atom, methyl, ethyl, isopropyl,
n-propyl, iso-butyl, n-butyl, 3-methylbutyl, cyclohexyl, and benzyl
group. More preferable examples of R include hydrogen atom, methyl,
ethyl, isopropyl, iso-butyl, 3-methylbutyl, and benzyl group. The
most preferable examples of R are hydrogen atom, methyl, isopropyl,
and benzyl group.
In an embodiment of the present invention, the reaction product of
the C.sub.1 to C.sub.8 aldehyde and the polyethylene polyamine
having 3 to 10 nitrogen atoms includes at least one saturated
heterocyclic compound having two nitrogen heteroatoms according to
formula (II).
In another embodiment of the present invention, the reaction
product of the C.sub.1 to C.sub.8 aldehyde and the polyethylene
polyamine having 3 to 10 nitrogen atoms includes at least one
saturated heterocyclic compound having two nitrogen heteroatoms
according to formula (II) and at least one saturated fused bicyclic
heterocyclic compound having two nitrogen heteroatoms according to
formula (III):
##STR00003## wherein X is independently selected from a hydrogen
atom, a linear or branched C.sub.1 to C.sub.4 alkyl group and a
substituted or un-substituted phenyl group, Y.sub.1 is a direct
bond or a divalent polyethylene polyamine group having 1 to 8
nitrogen atoms or a divalent polyethylene polyamine derivative
having 1 to 8 nitrogen atoms, R is independently a hydrogen atom or
a group selected from C.sub.1-C.sub.8 linear, cyclic, and branched
alkyl, alkenyl, and alkaryl groups, and Y.sub.2 is a direct bond or
a divalent polyethylene polyamine group having 1 to 7 nitrogen
atoms. The amine-epoxy curing agents can be used to cure, harden,
and/or crosslink multifunctional epoxy resins. The C.sub.1 to
C.sub.4 alkyl groups, the polyethylene polyamine groups having 1 to
8 nitrogen atoms, and the polyethylene polyamine groups having 1 to
7 nitrogen atoms may be branched or unbranched.
Y.sub.1 and Y.sub.2 are divalent polyethylene polyamine groups that
include repeating units that may be linear or branched. Suitable
repeating divalent polyethylene polyamine group units include the
following formula (IV):
##STR00004## wherein R is independently a hydrogen atom or a group
selected from C.sub.1-C.sub.8 linear, cyclic, and branched alkyl,
alkenyl, and alkaryl groups, and R from two consecutive repeating
units can form a 5- or 6-member ring with the backbone ethylene
unit, and n=1 to 8 for Y.sub.1 or n=1 to 7 for Y.sub.2.
In a preferred embodiment, the polyethylene polyamine having 3 to
10 nitrogen atoms (2a) comprises DETA and the the C.sub.1 to 08
aldehyde (2b) comprises formaldehyde. In this embodiment, the
reaction product of DETA and formaldehyde, which is the polyamine
component of the curing agent (2), comprises
1-(2-aminoethyl)imadazolidine. This corresponds to the case of
general formula (II) wherein X is a hydrogen atom, Y1, in a first
occurrence, is a divalent polyethylene polyamine group having 1
nitrogen, and in a second occurrence is a hydrogen atom, and where
R is a hydrogen atom in both occurrences. It also corresponds to
the case of general formula (IV) wherein R is a hydrogen atom and n
is 1, for Y.sub.1 in its first occurrence.
The polyamine component can comprise at least one multifunctional
amine. Multifunctional amine, as used herein, describes compounds
with amine functionality and which contain two (2) or more active
amine hydrogens.
Non-limiting examples of multifunctional amines that are within the
scope of the present invention include, but are not limited to, an
aliphatic amine, a cycloaliphatic amine, an aromatic amine, a
Mannich base derivative of an aliphatic amine, a cycloaliphatic
amine, or an aromatic amine, a polyamide derivative of an aliphatic
amine, a cycloaliphatic amine, or an aromatic amine, an amidoamine
derivative of an aliphatic amine, a cycloaliphatic amine, or an
aromatic amine, an amine adduct derivative of an aliphatic amine, a
cycloaliphatic amine, or an aromatic amine, and the like, or any
combination thereof.
More than one multifunctional amine can be used in the compositions
of the present invention. For example, the at least one
multifunctional amine can comprise an aliphatic amine and a Mannich
base derivative of a cycloaliphatic amine. Also, the at least one
multifunctional amine can comprise one aliphatic amine and one
different aliphatic amine.
Exemplary aliphatic amines include polyethyleneamines (ethylene
diamine (EDA), diethylene triamine (DETA), triethylenetetraamine
(TETA), tetraethylenepentamine (TEPA), and the like),
polypropyleneamines, aminopropylated ethylenediamines,
aminopropylated propylenediamines, 1,6-hexanediamine,
3,3,5-trimethyl-1,6-hexanediamine,
3,5,5-trimethyl-1,6-hexanediamine, 2-methyl-1,5-pentanediamine
(commercially available as Dytek-A), and the like, or combinations
thereof. Additionally, the poly(alkylene oxide) diamines and
triamines commercially available under the Jeffamine name from
Huntsman Corporation, are useful in the present invention.
Illustrative examples include, but are not limited to,
Jeffamine.RTM. D-230, Jeffamine.RTM. D-400, Jeffamine.RTM. D-2000,
Jeffamine.RTM. D-4000, Jeffamine.RTM. T-403, Jeffamine.RTM.
EDR-148, Jeffamine.RTM. EDR-192, Jeffamine.RTM. C-346,
Jeffamine.RTM. ED-600, Jeffamine.RTM. ED-900, Jeffamine.RTM.
ED-2001, and the like, or combinations thereof.
Cycloaliphatic and aromatic amines include, but are not limited to,
1,2-diaminocyclohexane, 1,3-diaminocyclohexane,
1,4-diaminocyclohexane, hydrogenated ortho-toluenediamine,
hydrogenated meta-toluenediamine, metaxylylene diamine,
hydrogenated metaxylylene diamine (referred to commercially as
1,3-BAC), isophorone diamine (IPDA), various isomers or norbornane
diamine, 3,3'-dimethyl-4,4'-diaminodicyclohexyl methane,
4,4'-diaminodicyclohexyl methane, 2,4'-diaminodicyclohexyl methane,
a mixture of methylene bridged poly(cyclohexyl-aromatic)amines, and
the like, or combinations thereof. The mixture of methylene bridged
poly(cyclohexyl-aromatic)amines is abbreviated as either MBPCAA or
MPCA, and is described in U.S. Pat. No. 5,280,091, which is
incorporated herein by reference in its entirety. In one aspect of
the present invention, the at least one multifunctional amine is a
mixture of methylene bridged poly(cyclohexyl-aromatic)amines
(MPCA).
Mannich base derivatives can be made by the reaction of the above
described aliphatic amines, cycloaliphatic amines, or aromatic
amines with phenol or a substituted phenol and formaldehyde. An
exemplary substituted phenol used to make Mannich bases with
utility in the present invention is cardanol, which is obtained
from cashew nut shell liquid. Alternatively, Mannich bases can be
prepared by an exchange reaction of a multifunctional amine with a
tertiary amine containing a Mannich base, such as
tris-dimethylaminomethylphenol (commercially available as
Ancamine.RTM. K54 from Air Products and Chemicals, Inc.) or
bis-dimethylaminomethylphenol.
Polyamide derivatives can be prepared by the reaction of an
aliphatic amine, cycloaliphatic amine, or aromatic amine with dimer
fatty acid, or mixtures of a dimer fatty acid and a fatty acid.
Amidoamine derivatives can be prepared by the reaction of an
aliphatic amine, cycloaliphatic amine, or aromatic amine with fatty
acids.
Amine adducts can be prepared by the reaction of an aliphatic
amine, cycloaliphatic amine, or aromatic amine with an epoxy resin,
for example, with the diglycidyl ether of bisphenol-A, the
diglycidyl ether of bisphenol-F, or epoxy novolac resins. The
aliphatic, cycloaliphatic, and aromatic amines also can be adducted
with monofunctional epoxy resins, such as phenyl glycidyl ether,
cresyl glycidyl ether, butyl glycidyl ether, other alkyl glycidyl
ethers, and the like.
In another aspect of the present disclosure, the curing agent
includes a co-curing agent. The co-curing agent may be an
amidoamine curing agent, an aliphatic curing agent, a polyamide
curing agent, a cycloaliphatic curing agent, or a Mannich base
curing agent which also includes phenalkamine.
Method of Making the Curing Agent Composition
In an embodiment, the curing agent comprises the reaction product
of: (1) a polyalkylene polyether modified polyepoxide resin
component, and (2) a polyamine component, which is the reaction
product of (2a) a polyethylene polyamine having 3 to 10 nitrogen
atoms and (2b) a C.sub.1 to C.sub.8 aldehyde. A preliminary step in
making the curing agent composition is producing the polyamine
component (2) by reacting the polyethylene polyamine compounds (2a)
with the aldehyde (2b). The reaction of the C.sub.1 to C.sub.8
aldehyde and the polyethylene polyamine compounds having 3 to 10
nitrogen atoms may proceed at a reaction temperature of about
-20.degree. C. to about 150.degree. C., about 0.degree. C. to about
120.degree. C., about 0.degree. C. to about 100.degree. C., about
0.degree. C. to about 90.degree. C., about 0.degree. C. to about
80.degree. C., about 20.degree. C. to about 100.degree. C., about
20.degree. C. to about 90.degree. C., about 20.degree. C. to about
80.degree. C., about 20.degree. C. to about 70.degree. C. The
reaction of the C.sub.1 to C.sub.8 aldehyde and the polyethylene
polyamine compounds is exothermic, thus, cooling might be necessary
to maintain reaction temperature at desired range.
Water is formed from the reaction of the aldehyde and the
polyethylene polyamine compounds, and is typically removed under
designated temperature and pressure. Water from the reaction may be
removed at different temperature and pressure than the condition
when the reaction of the aldehyde and the polyethylene polyamine
compounds takes place. The water formed may be removed by direct
atmosphere distillation or vacuum distillation, or removed by
forming azeotropic mixture with a solvent. Azeotropic solvent with
water includes, but is not limited to, toluene, xylene,
acetonitrile, n-butanol, isobutanol, and t-butanol, heptane, and
hexane. Suitable azeotropic solvents include toluene, xylene,
acetonitrile, and n-butanol.
The reaction of the C.sub.1 to C.sub.8 aldehyde and the
polyethylene polyamine compounds having 3 to 10 nitrogen atoms to
form the amine-epoxy curing agent of the present disclosure may be
conducted in a solvent media. Suitable solvent for the reaction
includes but is not limited to, water, acetonitrile, alcohol such
as methanol, ethanol, n-propanol, isopropanol, n-butanol, Dowanol
PM, t-butanol, isobutanol, and benzyl alcohol, and hydrocarbons
such as toluene, xylene, hexane, and heptane. Suitable reaction
solvent includes water, methanol, ethanol, n-propanol, isopropanol,
n-butanol, Dowanol PM and benzyl alcohol. The solvent may be
removed after the reaction is complete, or remain as part of the
curing agent. For example, benzyl alcohol may remain as plasticizer
for the curing agent.
The maximum mole ratio of the C.sub.1 to C.sub.8 aldehyde to the
polyethylene polyamine compounds having 3 to 10 nitrogen atoms is
half of the number of amine hydrogen, to 1, mathematically
expressed below:
.times..times..times..times..times..times..times..times..times.
##EQU00001##
The mole ratio of the C.sub.1 to C.sub.8 aldehyde to the
polyethylene polyamine compounds having 3 to 10 nitrogen atoms is
at least about 90%, or about 80%, or about 75%, or about 70%, or
about 65%, or about 60%, or about 55%, or about 50%, or about 45%,
or about 40%, or about 30%, or about 25%, or about 20%, or about
10% of the maximum mole ratio of the C1 to C8 aldehyde to the
polyethylene polyamine compounds having 3 to 10 nitrogen atom to
1.
The reaction to prepare the curing agent comprising the reaction
product of: (1) a polyalkylene polyether modified polyepoxide resin
component, and (2) a polyamine component, which is the reaction
product of (2a) a polyethylene polyamine having 3 to 10 nitrogen
atoms and (2b) a C.sub.1 to C.sub.8 aldehyde is conducted by
charging the polyamine component (2) to a reaction vessel, and
adding the polyalkylene polyether modified polyepoxide resin
component (1) at a controlled rate.
A curing agent comprising the reaction product of: (1) a
polyalkylene polyether modified polyepoxide resin component, and
(2) a polyamine component, which is the reaction product of (2a) a
polyethylene polyamine having 3 to 10 nitrogen atoms and (2b) a
C.sub.1 to C.sub.8 aldehyde can be produced with various reactant
ratios. It is within the scope of the present invention for the
stoichiometric ratio of the equivalent number of the active amine
hydrogens of the polyamine component (2) to the equivalent number
of epoxy groups in the polyalkylene polyether modified polyepoxide
resin component (1) to range from about 50:1 to about 2:1. In
another aspect, the ratio is about 40:1 to about 2:1, about 30:1 to
about 2:1, about 25:1 to about 2:1, about 20:1 to about 2:1, about
15:1 to about 2:1, about 10:1 to about 2:1, about 8:1 to about 2:1,
about 6:1 to about 2:1, about 5:1 to about 2:1, about 4:1 to about
2:1, or about 3:1 to about 2:1.
In accordance with the present invention, a method of making a
curing agent composition is provided. This method comprises adding
the polyalkylene polyether modified polyepoxide resin component (1)
to the polyamine component (2) at a controlled rate over a time
period generally from about 1 hour to about 4 hours. After the
addition step, the reaction can be allowed to continue for
approximately another 30 minutes to about 2 hours to provide for a
substantially complete reaction. The reaction can be done in a
reactor, vessel, or other container. The reaction may proceed at a
reaction temperature of about 20.degree. C. to about 160.degree.
C., about 20.degree. C. to about 150.degree. C., about 50.degree.
C. to about 150.degree. C., or about 50.degree. C. to about
140.degree. C. The temperature ranges during the addition step and
the following step to complete the reaction need not to be
identical, and can be different. Non-limiting examples of the
synthesis of curing agent compositions in accordance with the
present invention are illustrated in the examples.
In preparing the reaction product, the curing agent composition can
become very viscous, and in such cases, a solvent can be added to
the reactor. Exemplary solvents include, but are not limited to,
n-butanol, toluene, xylene, and the like, Dowanol.TM. solvents, or
mixtures thereof. The solvent can be removed via distillation after
the reaction is complete, and optionally replaced with water to
keep the viscosity low or to form an aqueous curing agent
composition.
In one aspect of the invention, before the reaction product cools,
at least one multifunctional amine having 2 or more active amine
hydrogens can be added to lower the viscosity and to target a
desired AHEW for the curing agent composition. Optionally, water is
added to reach a desired percent solids content for such aqueous
curing agent composition.
In an embodiment, the curing agent comprises (i) the reaction
product of: (1) a polyalkylene polyether modified polyepoxide resin
component, and (2) a polyamine component; and (ii) water.
In another embodiment, the curing agent comprises (i) the reaction
product of: (1) a polyalkylene polyether modified polyepoxide resin
component, and (2) a polyamine component; and (ii) at least one
multifunctional amine having 2 or more active amine hydrogens.
In another embodiment, the curing agent comprises (i) the reaction
product of: (1) a polyalkylene polyether modified polyepoxide resin
component, and (2) a polyamine component; (ii) at least one
multifunctional amine having 2 or more active amine hydrogens; and
(iii) water.
In another embodiment of the present invention, the curing agent
includes a co-curing agent. The co-curing agent may be an
amidoamine curing agent, an aliphatic curing agent, a polyamide
curing agent, a cycloaliphatic curing agent, or a Mannich base
curing agent which also includes phenalkamine. Generally, the
curing agent compositions have an amine hydrogen equivalent weight
(AHEW) based on 100% solids from about 30 to about 500. Further,
such curing agent compositions can have an AHEW based on 100%
solids in the range from about 50 to about 450, from about 50 to
about 400, from about 50 to about 350, from about 50 to about 300,
from about 50 to about 250, from about 50 to about 200, from about
100 to about 250, or from about 100 to about 200.
Amine-Epoxy Compositions
Generally, amine-epoxy coating compositions include a curing agent
and at least one multifunctional epoxy resin. An amine-epoxy
composition, in accordance with the present disclosure, includes,
in a first component, the curing agent as described above; and, in
a second component, an epoxy composition comprising at least one
multifunctional epoxy resin having at least two epoxide groups per
molecule. The at least one multifunctional epoxy resin having at
least two epoxide groups per molecule can be a liquid epoxy resin,
a solid epoxy resin, mixture of liquid and solid epoxy resin, and
can be used as neat without solvent, or as an aqueous epoxy
emulsion, or an aqueous solid epoxy dispersion. The curing agent in
accordance with the present disclosure can be used to cure, harden,
and/or crosslink the epoxy resin.
Multifunctional epoxy resins are well known to those of skill in
the art. One class of epoxy resins suitable for use in the present
invention comprises the glycidyl ethers of polyhydric phenols,
including the glycidyl ethers of dihydric phenols. Illustrative
examples include, but are not limited to, the glycidyl ethers of
resorcinol, hydroquinone,
bis-(4-hydroxy-3,5-difluorophenyl)-methane,
1,1-bis-(4-hydroxyphenyl)-ethane,
2,2-bis-(4-hydroxy-3-methylphenyl)-propane,
2,2-bis-(4-hydroxy-3,5-dichlorophenyl) propane,
2,2-bis-(4-hydroxyphenyl)-propane (commercially known as bisphenol
A), bis-(4-hydroxyphenyl)-methane (commercially known as bisphenol
F, and which may contain varying amounts of 2-hydroxyphenyl
isomers), and the like, or any combination thereof. Additionally,
advanced dihydric phenols of the following structure also are
useful in the present invention:
##STR00005## where m is an integer, and R.sub.1 is a divalent
hydrocarbon radical of a dihydric phenol, such as those dihydric
phenols listed above. Materials according to this formula can be
prepared by polymerizing mixtures of a dihydric phenol and
epichlorohydrin, or by advancing a mixture of a diglycidyl ether of
dihydric phenol. While in any given molecule the value of m is an
integer, the materials are invariably mixtures which can be
characterized by an average value of m, which is not necessarily a
whole number. Polymeric materials with an average value of m
between 0 and about 7 can be used in one aspect of the present
disclosure.
In another aspect, epoxy novolac resins, which are the glycidyl
ethers of novolac resins, can be used as multifunctional epoxy
resins in accordance with the present disclosure. In yet another
aspect, the at least one multifunctional epoxy resin is a
diglycidyl ether of bisphenol-A (DGEBA), an advanced or higher
molecular weight version of DGEBA, a diglycidyl ether of
bisphenol-F, an epoxy novolac resin, or any combination thereof.
Higher molecular weight versions or derivatives of DGEBA are
prepared by the advancement process, where excess DGEBA is reacted
with bisphenol-A to yield epoxy terminated products. The epoxy
equivalent weights (EEW) for such products range from about 450 to
3000 or more. Because these products are solid at room temperature,
they are often referred to as solid epoxy resins.
DGEBA or advanced DGEBA resins are often used in coating
formulations due to a combination of their low cost and generally
high performance properties. Commercial grades of DGEBA having an
EEW ranging from about 174 to about 250, and more commonly from
about 185 to about 195, are readily available. At these low
molecular weights, the epoxy resins are liquids and are often
referred to as liquid epoxy resins. It is understood by those
skilled in the art that most grades of liquid epoxy resin are
slightly polymeric, since pure DGEBA has an EEW of 174. Resins with
EEW's between 250 and 450, also generally prepared by the
advancement process, are referred to as semi-solid epoxy resins
because they are a mixture of solid and liquid at room temperature.
Generally, multifunctional resins with EEW's based on solids of
about 160 to about 750 are useful in the prevent invention. In
another aspect the multifunctional epoxy resin has an EEW in a
range from about 170 to about 250.
The relative amount chosen for the epoxy composition versus that of
the curing agent composition, can vary depending upon, for example,
the end-use article, its desired properties, and the fabrication
method and conditions used to produce the end-use article. For
instance, in coating applications using certain amine-epoxy
compositions, incorporating more epoxy resin relative to the amount
of the curing agent composition, can result in coatings which have
increased drying time, but with increased hardness and improved
appearance as measured by gloss. Amine-epoxy compositions of the
present invention generally have stoichiometric ratios of epoxy
groups in the epoxy composition to amine hydrogens in the curing
agent composition ranging from about 1.5:1 to about 0.7:1. For
example, such amine-epoxy compositions can have stoichiometric
ratios of epoxy to amine hydrogen from about 1.5:1 to about 0.7:1,
or about 1.4:1 to about 0.7:1, or about 1.3:1 to about 0.7:1, or
about 1.2:1 to about 0.7:1, or about 1.1:1 to about 0.7:1, or about
1.0:1 to about 0.7:1, or about 0.9:1 to about 0.7:1, or about 1.2:1
to about 0.8:1, or about 1.1:1 to about 0.9:1.
Optionally, other additives may be present in the amine-epoxy
composition. If desired, either one or both of the amine curing
agent and curable epoxy resin composition may be mixed, before
curing, with one or more customary additives, for example, a
stabilizer, extender, filler, reinforcing agent, pigment, dyestuff,
plasticizer, tackifier, rubber, accelerator, diluent or any mixture
thereof. Other customary additives can include, but are not limited
to, solvents (including water), accelerators, plasticizers,
fillers, fibers such as glass or carbon fibers, pigments, pigment
dispersing agents, rheology modifiers, and thixotropes.
Compositions in accordance with the present invention can comprise
at least one multifunctional amine. Multifunctional amine, as used
herein, describes compounds with amine functionality and which
contain two (2) or more active amine hydrogens.
Articles
The present invention also is directed to articles of manufacture
comprising the compositions disclosed herein. For example, an
article can comprise an amine-epoxy composition which comprises the
reaction product of a curing agent composition and an epoxy
composition. Articles of manufacture produced from amine-epoxy
compositions disclosed herein include, but are not limited to,
adhesives, coatings, primers, sealants, curing compounds,
construction products, flooring products, and composite products.
Further, such coatings, primers, sealants, or curing compounds can
be applied to metal or cementitious substrates. Coatings based on
these amine-epoxy compositions can be solvent-free or can contain
diluents, such as water or organic solvents, as needed for the
particular application. Coatings can contain various types and
levels of pigments for use in paint and primer applications.
Amine-epoxy coating compositions comprise a layer having a
thickness ranging from 40 to 400 .mu.m (micrometer), preferably 80
to 300 .mu.m, more preferably 100 to 250 .mu.m, for use in a
protective coating applied on to metal substrates. In addition, for
use in a flooring product or a construction product, coating
compositions comprise a layer having a thickness ranging from 50 to
10,000 .mu.m, depending on the type of product and the required
end-properties.
Numerous substrates suitable for the application of coatings of the
present invention include, but are not limited to, concrete and
various types of metals and alloys, such as steel and aluminum.
Coatings of the present invention are suitable for the painting or
coating of large metal objects or cementitious substrates including
ships, bridges, industrial plants and equipment, and floors.
Coatings of this invention can be applied by any number of
techniques including spray, brush, roller, paint mitt, and the
like. In order to apply very high solids content or 100% solids
coatings of the present disclosure, plural component spray
application equipment can be used, in which the amine and epoxy
components are mixed in the lines leading to the spray gun, in the
spray gun itself, or by mixing the two components together as they
leave the spray gun. Using this technique can alleviate limitations
with regard to the pot life of the formulation, which typically
decreases as both the amine reactivity and the solids content
increases. Heated plural component equipment can be employed to
reduce the viscosity of the components, thereby improving ease of
application.
Construction and flooring applications include compositions
comprising the amine-epoxy compositions of the present invention in
combination with cement, concrete or other materials commonly used
in the construction industry. Applications of compositions of the
present invention include, but are not limited to use of the
composition as a primer, a deep penetrating primer, a coating, a
curing compound, and/or a sealant for new or old concrete. As a
primer or a sealant, the amine-epoxy compositions of the present
disclosure can be applied to surfaces to improve adhesive bonding
prior to the application of a coating. Crack injection and crack
filling products also can be prepared from the compositions
disclosed herein. Amine-epoxy compositions of the present invention
can be mixed with cementitious materials such as cement or concrete
mix to form epoxy modified cements, tile grouts, and the like.
The epoxy modified cement composition may be used for coating,
adhesive, sealer, grouting and mortar. Particularly, it is suitable
for a mortar or coating, more particularly used for self-leveling
floor coating.
The epoxy modified cement composition, according to the present
invention, includes a combination of (A) an epoxy composition
comprising at least one multifunctional epoxy resin having at least
two epoxide groups per molecule, (B) a curing agent comprising
water and the reaction product of: (1) a polyalkylene polyether
modified polyepoxide resin component, and (2) a polyamine
component, which is the reaction product of (2a) a polyethylene
polyamine having 3 to 10 nitrogen atoms and (2b) a C.sub.1 to
C.sub.8 aldehyde, and (C) a solid component comprising at least one
hydraulic inorganic binder. The hydraulic inorganic binder can be
cement.
The epoxy modified cement composition includes a curing agent of
the present invention in a sufficient concentration and in a ratio
such that a cured epoxy modified cement solid article formed from
the epoxy modified cement composition has a compressive strength
greater than about 6,000 psi as measured by ASTM C-539. The
compressive strength in one embodiment is measured at 7 days after
application of the epoxy modified cement composition. In another
embodiment, the compressive strength is measured 28 days after the
application of the epoxy modified cement composition.
The invention is further illustrated by the following examples,
which are not to be construed as imposing limitations to the scope
of this invention. Various other aspects, embodiments,
modifications, and equivalents thereof which, after reading the
description herein, may suggest themselves to one of ordinary skill
in the art without departing from the spirit of the present
invention or the scope of the appended claims.
EXAMPLES
The following synthesis examples are provided to illustrate certain
aspects or embodiments of the instant invention and shall not limit
the scope of the claims appended hereto.
Synthesis Examples
Diethylenetriamine (DETA) and formaldehyde aqueous solution were
purchased from Aldrich. The reaction product was analyzed by gas
chromatography (GC) to determine the amount of unreacted DETA,
Metrohm titrator using Karl Fisher titration method for residual
water content, Brookfield viscometer for viscosity, Metrohm
titrator for amine value, and nuclear magnetic resonance (NMR) for
chemical composition. The NMR experiments were performed at ambient
temperature employing the Bruker DRX-400 FT-NMR spectrometer
equipped with a 10 mm BBO probe. Quantitative .sup.13C NMR data was
acquired using inverse-gated decoupling, a 45.degree. pulse, and a
6 second relaxation delay. The samples were dissolved in
chloroform-d with chromium acetylacetonate added as a relaxation
agent. The chemical shift scale was referenced to the solvent peak.
GC analysis was performed on Agilent 7890 Gas Chromatograph
equipped with a Agilent CP-Volamine 0.32 mm.times.30 m--column and
a Flame Ionization Detector. The samples were prepared as 1%
solutions in isopropanol then placed in 2 mL autosampler vials for
GC analysis. Standard solutions ranging from 0.005 to 0.51 wt %
DETA in isopropanol were used to create a six point external,
linear calibration curve to quantify the residual DETA in the
samples. The square of correlation coefficient (R.sup.2) value for
the calibration curves are 0.999.
Example 1. Synthesis of Polyamine 1 (PA1): Reaction Product of DETA
with Formaldehyde at Molar Ratio of 1.60:1 Formaldehyde to DETA
DETA (650 g) was charged to a reactor equipped with a nitrogen
inlet, a condenser, an addition funnel, and an overhead stirrer. To
DETA was added formaldehyde aqueous solution (818.1 g) via an
addition funnel to maintain a temperature below 60.degree. C. After
the addition, the reaction was kept at 60.degree. C. for 30
minutes. Water was then removed under reduced pressure. The product
was obtained as a clear liquid in quantitative yield with an amine
value of 857 meqKOH/g, viscosity of 9,470 mPas at 25.degree. C.,
water content of 0.41%, and residual DETA of 1.3%. NMR analysis
showed that 39 mol % of DETA formed 1-(2-aminoethyl)imidazolidine,
which corresponds to 37 wt % to the total weight in the product by
calculation.
Example 2. Synthesis of Polyalkylene Polyether Modified Polyepoxide
Resin A Via Polyalkylene Polyether Polyol
Polyethylene glycol 1000 (379 g) and 490 g of a bisphenol-A
diglycidyl ether having an epoxy equivalent weight of 190 were
charged to a stirred reactor equipped with a thermocouple and a
reflux condenser. A catalyst, BF.sub.3-amine complex, commercially
available from Air Products and Chemicals, Inc., as Anchor.RTM.
1040 (3 g) was added to the reactor. While the reactor contents
were stirred, the reactor temperature was increased to 140.degree.
C. This temperature was maintained until the epoxy equivalent
weight increased to about 475 to 500. The reactor contents were
then cooled, resulting in a reaction product designated as Resin A.
The epoxy equivalent weight of Resin A was 480 and the viscosity at
40.degree. C. was 33 Poise (3.3 Pa-s).
Example 3. Synthesis of Polyalkylene Polyether Modified Polyepoxide
Resin B Via Polyalkylene Polyether Polyol
Example 3 utilized the same process as described in Example 2. The
reactants were 3043.8 g of polyethylene glycol 2000 and 1144.6 g of
a bisphenol-A diglycidyl ether having an epoxy equivalent weight of
190. After following the process of Example 2, the final product
was designated as Resin B. The epoxy equivalent weight of Resin B
was 1392 and the viscosity at 70.degree. C. was 668 mPas. Viscosity
was determined using a Brookfield DV-II+ cone and plate viscometer,
CP52 spindle, 100 rpm. Using Gel Permeation Chromatography (GPC),
THF solvent, and polystyrene calibration standards, the M.sub.n
(number-average molecular weight) was 4017, and the M.sub.w (weight
average molecular weight) was 7866. Low molecular weight unreacted
epoxy resin was excluded from molecular weight distribution and
from the determination of M.sub.n and M.sub.w.
Example 4. Synthesis of Polyalkylene Polyether Modified Polyepoxide
Resin C Via Poly(Alkylene Oxide) Mono-Amine
A reactor was equipped with a nitrogen inlet, a condenser, an
addition funnel, and an overhead stirrer. Epoxy resin Epon 828 (250
g) was charged to the reactor. The content was heated up to
80.degree. C. Jeffamine M1000 amine (available from the Huntsman
Corp., AHEW of 489 mgKOH/eq) (214.5 g) was melted at 70.degree. C.
oven and charged to an addition funnel. Jeffamine M1000 was then
charged to the Epon 828 resin in the reactor over about 30 minutes
to keep temperature below 95.degree. C. The temperature was raised
to 95.degree. C. and held at that temperature for 1 hour. The
product Resin C was obtained as a clear liquid and has a viscosity
of 8,650 cPs, and an EEW of 409.
Example 5. Synthesis of Polyalkylene Polyether Modified Polyepoxide
Resin D Via Poly(Alkylene Oxide) Mono-Amine
Example 5 utilized the same process as described in Example 4. The
reactants were Jeffamine 2070 (available from the Huntsman Corp.,
AHEW of 1040 mgKOH/eq) (273.7 g) and Epon 828 (150 g). The product
Resin D was obtained as clear liquid and has an EEW of 578.
Example 6. Synthesis of Curing Agent 1 (CA1) from Polyamine PA1 of
Example 1 and Resin A of Example 2
Polyamine PA1 of example 1 (169.4 g) was charged to a reactor
equipped with a nitrogen inlet, a condenser, an addition funnel,
and an overhead stirrer. The content was heated up to 80.degree. C.
Resin A of example 2 (127.1 g) was warmed up to 80.degree. C. and
added to an addition funnel. Resin A was charged to a reactor over
about 40 minutes to keep temperature below 95.degree. C. The
temperature was raised to 95.degree. C. and held at that
temperature for 1 hour. Water (198 g) was then added to the
reaction under vigorous stirring. The product curing agent 1 (CA1)
was obtained as a clear liquid at 60% solid and has a viscosity of
3,850 cPs, and an amine value of 315 mg KOH/g, and a calculated
AHEW of 222.
Example 7. Synthesis of Curing Agent 2 (CA2) from Polyamine PA1 of
Example 1 and Resin C of Example 4
Example 7 utilized the same process as described in Example 6. The
reactants were polyamine PA1 of example 1 (166.7 g), Resin C of
example 4 (125 g) and water (194 g). The product curing agent 2
(CA2) was obtained as a clear liquid and at 60% solid has an amine
value of 320 mgKOH/g, and a calculated AHEW of 226.
Example 8. Synthesis of Curing Agent 3 (CA3) from Polyamine PA1 of
Example 1 and Isophorone Diamine with Resin A of Example 2
Example 8 utilized the same process as described in Example 6. The
reactants were polyamine PA1 of example 1 (60.3 g), isophorone
diamine (obtained from Aldrich, 112 g), Resin A of example 2 (241.2
g) and water (338.4 g). The product curing agent 3 (CA3) was
obtained as a clear liquid and at 55% solid and has a viscosity of
8,590 cPs, and an amine value of 169 mgKOH/g, and a calculated AHEW
of 249.
Example 9. Synthesis of Curing Agent 4 (CA4) from Polyamine PA1 of
Example 1 and Isophorone Diamine with Resin C of Example 4
Example 9 utilized the same process as described in Example 6. The
reactants were polyamine PA1 of example 1 (56.6 g), isophorone
diamine (obtained from Aldrich, 105 g), Resin C of example 4 (226
g) and water (194 g). The product curing agent 4 (CA4) was obtained
as a clear liquid and at 55% solid and has a viscosity of 5,250
cPs, an amine value of 177 mgKOH/g, and a calculated AHEW of
257.
Example 10. Synthesis of Curing Agent 5 (CA5) from Polyamine PA1 of
Example 1 and Isophorone Diamine with Resin A of Example 2
Example 10 utilized the same process as described in Example 6. The
reactants were isophorone diamine (obtained from Aldrich, 94.5 g),
Resin A of example 2 (165.4 g) and water (260 g). The product
curing agent 5 (CA5) was obtained as a clear liquid and at 50%
solid and has a viscosity of 39,230 cPs, an amine value of 121
mgKOH/g, and a calculated AHEW of 277.
Example 11. Synthesis of Curing Agent 6 (CA6) from Polyamine PA1 of
Example 1 and Isophorone Diamine with Resin A of Example 2
Example 11 utilized the same process as described in Example 6. The
reactants were polyamine PA1 of example 1 (87.7 g), isophorone
diamine (obtained from Aldrich, 95.2 g), Resin A of example 2
(232.5 g) and water (339 g). The product curing agent 6 (CA6) was
obtained as clear liquid and at 55% solid and has a viscosity of
30,650 cPs, and an amine value of 175 mgKOH/g, and a calculated
AHEW of 248.
Example 12. Synthesis of Curing Agent 7 (CA7) from Polyamine PA1 of
Example 1 and Isophorone Diamine with Resin C of Example 4
Example 12 utilized the same process as described in Example 6. The
reactants were polyamine PA1 of example 1 (83.2 g), isophorone
diamine (obtained from Aldrich, 90 g), Resin C of example 4 (219.8
g) and water (324 g). The product curing agent 7 (CA7) was obtained
as a clear liquid and at 55% solid and has a viscosity of 3,637
cPs, and an amine value of 197 mgKOH/g, and a calculated AHEW of
255.
Example 13. Synthesis of Curing Agent 8 (CA8) from Polyamine PA1 of
Example 1 and Isophorone Diamine with Resin A of Example 2
Example 13 utilized the same process as described in Example 6. The
reactants were polyamine PA1 of example 1 (14.8 g), isophorone
diamine (obtained from Aldrich, 130.5 g), Resin A of example 2
(240.2 g) and water (383 g). The product curing agent 8 (CA8) was
obtained as a clear liquid and at 50% solid and has a viscosity of
21,320 cPs, and an amine value of 131 mgKOH/g, and a calculated
AHEW of 276.
Example 14. Synthesis of Curing Agent 9 (CA9) from Polyamine PA1 of
Example 1 and Isophorone Diamine with Resin C of Example 4
Example 14 utilized the same process as described in Example 6. The
reactants were polyamine PA1 of example 1 (13.9 g), isophorone
diamine (obtained from Aldrich, 125.4 g), Resin C of example 4
(229.6 g) and water (368 g). The product curing agent 9 (CA9) was
obtained as a clear liquid and at 50% solid and has a viscosity of
12,820 cPs, and an amine value of 136 mgKOH/g, and a calculated
AHEW of 285.
Example 15. Synthesis of Curing Agent 10 (CA10) from Polyamine PA1
of Example 1 and Isophorone Diamine with Resin a of Example 2
Example 15 utilized the same process as described in Example 6. The
reactants were polyamine PA1 of example 1 (30 g), isophorone
diamine (obtained from Aldrich, 120 g), Resin A of example 2 (237.2
g) and water (388 g). The product curing agent 10 (CA10) was
obtained as a clear liquid and at 50% solid and has a viscosity of
14,900 cPs, and an amine value of 135 mgKOH/g, and a calculated
AHEW of 276.
Example 16. Synthesis of Curing Agent 11 (CA11) from Polyamine PA1
of Example 1 and Isophorone Diamine with Resin C of Example 4
Example 16 utilized the same process as described in Example 6. The
reactants were polyamine PA1 of example 1 (28.8 g), isophorone
diamine (obtained from Aldrich, 115.4 g), Resin C of example 4
(223.12 g) and water (368 g). The product curing agent 11 (CA11)
was obtained as a clear liquid and at 50% solid and has a viscosity
of 7,390 cPs, and an amine value of 147 mgKOH/g, and a calculated
AHEW of 285.
Testing of Curing Agents
Epon 828 (EEW 190) liquid epoxy resin, solid resin dispersions
Ancarez AR555 (obtained from Evonik Corporation, 55% solid, EEW
550), and Epodil 748 (obtained from Evonik Corporation, EEW 290)
were used for the test. The test methods are outlined in Table 1.
Anquamine 721 (A721) is a waterborne curing agent based on
alkylated aliphatic amine-epoxy adduct, and has a viscosity of
40,000 cPs. Anquamine 401 (A401) is a waterborne curing agent based
on aliphatic amine-epoxy adduct and has a viscosity of 30,000 cPs
at 70% solid. Both are available from Evonik Corporation.
TABLE-US-00001 TABLE 1 General Test Methods Property Measurements
ASTM METHOD Drying time (hours) BK recorder Thin film set times
D5895 Phase 1: set to touch Phase 2: tack free Phase 3: dry hard
Coating Appearance Gloss (20.degree.)/gloss (60.degree.) D523
Solvent Resistance MEK Double Rubs D7835/D7835M Hardness Persoz
Pendulum Hardness (s) D4366 Shore D D2240
Test Examples of Curing Agents
Test Example 1. The Thin Film Set Time (TFST) of Coatings Using
Liquid Epoxy Resin Epon 828, and Resin Dispersion AR555
The thin film set time was determined using a Beck-Koller recorder,
in accordance with ASTM D5895. The amine-epoxy coatings were
prepared on standard glass panels at a wet film thickness of about
150 micron WFT (wet film thickness) using a Bird applicator. The
coatings were cured at 23.degree. C./50% relative humidity (RH),
and 10. .degree. C./60% relative humidity (RH). The data are
summarized in Table 2. The curing agent of the present invention
has low viscosity and the coatings containing the curing agent of
the present invention shows much faster thin film set time at
23.degree. C. and 10.degree. C.
TABLE-US-00002 TABLE 2 Thin film set time using CA1 with liquid
epoxy resin Curing agents CA1 A721 A401 CA1 CA1 Solid % 60% 50% 70%
60% 60% phr 120 160 70 140 36 Resin Epon 828 Epon 828 Epon 828 Epon
828 AR555 Thin film set 23.degree. C. 23.degree. C. 23.degree. C.
10.degree. C. 10.degree. C. time (h) Stage 1 0.9 2 2.3 0.8 0.5
Stage 2 1.3 3.5 3.4 1.3 0.8 Stage 3 2.4 5.5 5.1 5.3 3.8
Test Example 2: Solvent Resistance Test
The clear epoxy-amine coating compositions using the present
invention was tested for MEK double rub. The MEK double rub test is
an indicator of how well the through cure properties of the film
have developed. The higher the number of MEK double rubs, then the
grater the film integrity. The coating made from CA1 and Ancarez
AR555 was applied on cold-rolled steel substrate at 150 microns wet
film thickness, and cured at 23.degree. C. and 50% RH for 5 days.
The coating easily passed >200 MEK double rub test.
Test Example 3: Coating Properties of Clear Coats Using the Curing
Agents of the Present Invention
The curing agents and epoxy resin were mixed at the phr described
in Table 3, and further diluted with water to a mix viscosity of
about 200 cPs. Clear coatings were applied onto glass substrate at
150 microns wet film thickness and cured at 23.degree. C. and 50%
RH. The coatings were evaluated for Persoz hardness at 1 day (d1)
and 7 day (d7) and gloss during potlife. Also viscosity build
during potlife and drying times were determined. The data are
summarized in Table 3 and clearly show that the curing agents of
the present invention provide coatings with fast dry time and
hardness development with both liquid epoxy resin and solid epoxy
resion dispersion.
TABLE-US-00003 TABLE 3 Coating properties of clear coats Curing
agent CA1 CA1 CA3 CA4 CA6 resin Epon 828 AR555 AR555 AR555 AR555
phr 140 38 34 35 34 solid % 45% 50% 44% 46% 42% Viscosity 0'' 160
180 220 220 210 (cPs) 10'' 220 210 160 160 150 20'' 290 240 120 120
110 30'' 650 320 120 120 90 40'' 2500 460 100 100 80 50'' 880 80 80
70 60'' 70 70 90 70'' 60 60 60 80'' 50 50 50 90'' 80 80 60
20.degree. 60.degree. 20.degree. 60.degree. 20.degree. 60.degree.
20.deg- ree. 60.degree. 20.degree. 60.degree. Specular 10'' 48 73
135 127 159 137 159 137 132 130 gloss 20'' 45 71 136 127 167 140
167 140 156 136 (GU) 30'' 29 56 134 128 166 139 166 139 166 140
40'' 23 48 135 128 153 134 153 134 157 136 50'' 92 115 149 133 149
133 154 135 60'' 148 133 148 133 149 133 70'' 137 128 137 128 153
134 80'' 125 122 125 122 143 131 90'' 132 126 132 126 132 127 d1 d7
d1 d7 d1 d7 d1 d7 d1 d7 Persoz 10'' 243 291 200 278 173 307 173 307
161 287 hardness 20'' 255 283 199 290 199 316 199 316 173 293 (s)
30'' 236 280 211 288 214 324 214 324 189 311 40'' 256 291 217 300
228 334 228 334 205 312 50'' 195 276 235 336 235 336 211 320 60''
247 339 247 339 222 324 70'' 250 344 250 344 230 330 80'' 252 341
252 341 231 334 90'' 259 344 259 344 231 328 Thin film ph1 0.40
0.40 0.5 0.5 0.4 set time ph2 0.60 0.80 0.8 0.8 0.6 (h) ph3 0.80
1.40 1 1 1 Curing agent CA7 CA8 CA9 CA10 CA11 resin AR555 AR555
AR555 AR555 AR555 phr 35 38 39 38 39 solid % 49% 45% 45% 45% 45%
Viscosity 0'' 210 220 220 210 210 (cPs) 10'' 150 120 120 120 120
20'' 110 100 100 100 100 30'' 90 90 90 80 80 40'' 80 100 100 70 70
50'' 70 100 100 50 50 60'' 90 80 80 80 80 70'' 60 90 90 70 70 80''
50 80 80 60 60 90'' 60 70 70 80 80 20.degree. 60.degree. 20.degree.
60.degree. 20.degree. 60.degree. 20.deg- ree. 60.degree. 20.degree.
60.degree. Specular 10'' 132 130 169 140 169 140 168 139 168 139
gloss 20'' 156 136 168 139 168 139 159 136 159 136 (GU) 30'' 166
140 166 138 166 138 164 138 164 138 40'' 157 136 153 134 153 134
162 137 162 137 50'' 154 135 156 135 156 135 156 135 156 135 60''
149 133 138 129 138 129 137 129 137 129 70'' 153 134 139 129 139
129 128 125 128 125 80'' 143 131 139 129 139 129 138 129 138 129
90'' 132 127 126 123 126 123 131 125 131 125 d1 d7 d1 d7 d1 d7 d1
d7 d1 d7 Persoz 10'' 161 287 162 292 162 292 169 303 169 303
hardness 20'' 173 293 189 308 189 308 194 315 194 315 (s) 30'' 189
311 192 319 192 319 209 318 209 318 40'' 205 312 209 329 209 329
215 326 215 326 50'' 211 320 217 330 217 330 208 331 208 331 60''
222 324 228 290 228 290 232 333 232 333 70'' 230 330 237 337 237
337 238 301 238 301 80'' 231 334 231 332 231 332 243 311 243 311
90'' 231 328 236 338 236 338 248 329 248 329 Thin film ph1 0.4 0.3
0.3 0.5 0.5 set time ph2 0.6 0.5 0.5 0.8 0.8 (h) ph3 1 0.8 0.8 1
1
Test Example 4: Test of Adhesion to Dry and Wet Concrete Using the
Curing Agents of Present Invention in Primer Formulations
B25 (based on DIN 1045) concrete blocks were used for the test.
Prior to conducting any test, the concrete blocks were prepared for
by removing any loose concrete with a wire brush followed by vacuum
cleaning to remove any dust. For dry concrete adhesion test, they
were conditioned at 10.degree. C./60% RH in order to attain the
testing temperature prior to the primer application.
For wet concrete adhesion test, the concrete blocks were placed in
a container with water on supports making sure the water level was
approximately 1 cm below the tile surface and water was able to
circulate underneath the blocks. Excess water was removed from the
surface before the primer application.
Prior to primer application, the surface temperature of the
concrete blocks was determined using infrared thermometer and the
moisture content of the concrete was determined using Testo 606-1
hygrometer, preset material 3 (concrete). For dry concrete adhesion
test, the surface temperature is about 10.degree. C. for both wet
and dry concrete and moisture content of 2% for dry test, and 3.4%
for wet test.
The primer composition was specified in Table 4 and Table 5, and
further diluted with water to a mix viscosity of about 200 cPs. The
primer was applied onto the concrete blocks by brush at application
thickness of 400 g/m.sup.2. After application, the drying process
was followed by thumb twist drying time until the primer was dry
hard. The primer was then left to cure for 7 days before measuring
the pull off adhesion.
Before the adhesion testing, a trench was drilled through the
coating and the coating surface was lightly sanded. Dollies were
glued onto the dust free coating surface using Loctite 3425 epoxy
glue obtained from Manutan. 6 Dollies were tested for each primer
sample. The glue was left to cure for 1 day and dollies were pulled
off using a PAT-adhesion tester. Both the tensile stress at break
and the type of failure were recorded, and summarized in Table 4
and Table 5. The data clearly demonstrate that the curing agents of
the present invention provide coatings with fast dry time at low
temperature on wet and dry concrete, and good adhesion to
concrete.
TABLE-US-00004 TABLE 4 Performance properties of primers on dry
concrete at low temperature (10.degree. C./ 60% RH) at coating
thickness of 400 g/m.sup.2 Curing agent blend of blend of CA1/CA5
CA1/CA5 33%/67% 33%/67% CA1 CA1 wt wt CA3 CA4 CA9 CA10 resin AR555
Epon 828/ Epon 828/ AR555 AR555 AR555 AR555 AR555 Epodil 748 Epodil
748 90/10 90/10 phr 30 143 132 47 34 35 39 38 solid % 56% 71% 73%
47% 44% 46% 45% 45% Thumb twist 6 6 9-10 3.5 2.3 3.8 4.5 2 drying
time.sup.1 Tensile stress 7.1 8.5 9 7.4 6.5 6.3 7.5 7.4 to
break.sup.2 Type of failure.sup.3 100% A 100% A 100% A 97% A; 3% AB
72% A; 93% A; 76% A; 100% A 28% AB 7% AB 24% AB .sup.1Coating on
B25 concrete block, stages rated according to ASTM D 1640
.sup.2Determined using PAT adhesion tester, ISO 4624 .sup.3A =
cohesive failure of substrate; A/B = adhesive failure between
substrate and first coat;
TABLE-US-00005 TABLE 5 Performance properties of primers on wet
concrete at low temperature (10.degree. C./ 60% RH) at coating
thickness of 400 g/m.sup.2 Curing agent blend of blend of CA1/CA5
CA1/CA5 33%/67% 33%/67% CA1 wt wt CA3 CA4 CA9 CA10 resin Epon 828/
Epon 828/ AR555 AR555 AR555 AR555 AR555 Epodil 748 Epodil 748 90/10
90/10 phr 143 132 47 34 35 39 38 solid % 71% 73% 47% 44% 46% 45%
45% Thumb twist drying 8-24 8-24 4.5 2.3 2 3.8 4.5 time.sup.1
Tensile stress 5.8 6.5 4.7 6.5 6.3 7.5 7.4 to break.sup.2 Type of
failure.sup.3 95% A; 5% AB 98% A; 2% AB 98% A; 2% AB 97% A; 72% A;
93% A; 76% A; 3% AB 28% AB 7% AB 24% AB .sup.1Coating on B25
concrete block, stages rated according to ASTM D 1640
.sup.2Determined using PAT adhesion tester, ISO 4624 .sup.3A =
cohesive failure of substrate; A/B = adhesive failure between
substrate and first coat;
Test Example 5: Evaluation of White Paint Formulations Using the
Curing Agents of the Present Invention
White paint formulations were prepared according to the amounts
specified in Table 6. Part A was prepared first. Components 1a to 3
were mixed at low shear until homogeneous, then components 4 and 5
were added and mixed at low shear until homogeneous, followed by
grinding at high speed. Component 6 was added to adjust viscosity.
Part B was added to Part A and mixed mechanically for 1-2 minutes
until homogeneous.
Coatings based on above paint formulations were applied at 225
microns wet film thickness glass panels through potlife and basic
performance parameters were determined after 1 day (d1) and 7 days
(d7). Mix viscosity was determined in time to determine the potlife
of the paint formulations. Also thin film set time was determined
and Persoz hardness and gloss were followed during potlife. The
data are summarized in Table 7.
Paint flocculation was tested by filling a 100 mL bottle with 50 mL
of de-mineralized water and adding 5 drops of the white paint
formulation. The bottle was then shaken and put upside down to
assess if any particles were present on the bottle walls.
The data in Table 7 clearly demonstrate that the white paint
formulations using the curing agent of the present invention are
very stable and provide semi-glossy white paint with fast dry time,
and hardness development.
TABLE-US-00006 TABLE 6 White paint formulations White paint 1 White
paint 2 A 1a CA5 12.17 10.14 1b CA1 3.08 4.96 2 Zetasperse 3800
0.54 0.55 3 Surfynol DF-62 0.05 0.05 4 Kronos 2160 (TiO2) 12.63
12.87 5 Tafigel PUR 55 (thickner) 0.32 0.32 6 Water 9.9 10.11 B 7
Epon 828 10.2 10.4 8 Epodil 748 1.1 1.1
TABLE-US-00007 TABLE 7 White paint formulation data summary White
Paint 1 White Paint 2 Additional water (g) 7 6 Mix viscosity
(cPs).sup.1 0'' 230 240 15'' 170 250 30'' 190 220 60'' 180 240 90''
210 250 120'' 210 300 150'' 260 320 20.degree. 60.degree.
20.degree. 60.degree. Specular gloss (GU) 15'' 78 95 53 88 30'' 80
96 58 90 60'' 87 96 64 92 90'' 86 96 62 90 120'' 85 95 50 84 150''
82 94 36 77 d 1 d 7 d 1 d 7 Persoz hardness (s) 15'' 97 242 119 249
30'' 114 240 127 249 60'' 145 277 154 274 90'' 168 288 176 271
120'' 176 268 183 273 150'' 183 283 195 274 Thin film set time (h)
ph 1 1.3 0.8 ph 2 3 1.8 ph 3 4 2.5 Flocculation test pass pass
Test Example 6: Cement Stability of the Amine-Epoxy Compositions
Using the Curing Agents of the Present Invention
Table 8 summarizes the amine-epoxy compositions using the curing
agents of the present invention at 10% solids. Cement stability
testing was conducted by mixing the amine-based curing agent, epoxy
resin, and water to achieve 10% solids, as indicated in Table 8. To
this diluted amine-epoxy composition at 10% solids, 1 g of Portland
cement was added and mixed thoroughly. Many commercially available
amine-epoxy emulsions do not remain stable upon addition of the
cement and the increase in alkalinity, and tend to curdle. Table 8
shows that each of the amine-epoxy compositions, exhibited a stable
emulsion after addition of the cement.
TABLE-US-00008 TABLE 8 Cement stability test CA1 CA2 CA3 CA4 CA6
CA7 CA8 CA9 CA10 CA11 curing agent 3.43 3.48 3.81 3.88 3.80 3.87
4.21 4.29 4.21 4.29 (g) Epon 828 resin 2.94 2.91 2.91 2.87 2.91
2.87 2.90 2.86 2.90 2.86 (g) Water (g) 43.63 43.61 43.29 43.25
43.29 43.26 42.90 42.86 42.90 42.86 Cement stability stable stable
stable stable stable stable stable stable s- table stable
Test Example 7: Epoxy Modified Cement Compositions Using the Curing
Agents of the Present Invention
The composition of epoxy modified cement is shown in Table 9, and
Table 10 illustrates the composition of Part A. The components in
Part A were emulsified to achieve a stable emulsion. Part B was
premixed at least 24 hours prior to compounding, then Part A was
added. Part C was premixed before adding to the Part A and Part B
mixture. Working time, flowability, compressive strength, and shore
D hardness were tested.
For comparison, a commercially available urethane modified cement
system FasTop 12 S-Urethnane Slurry System from Sherwin Williams
was prepared, and the composition is shown in Table 11. Part A and
Part B were mixed with low speed drill, then Part C was added and
mixed until homogeneous.
Shore D samples were prepared in a 6''.times.9''.times.1/2'' mold.
The compressive strength was determined according to ASTM C-579
with a cylinder of 1 inch diameter by 1 inch height. The samples
were cured at 23.degree. C. and 50% RH. The flowability and working
time tests were conducted by filling the samples into a circular
mold with a dimension of 3 inches diameter and 11/4 inches height.
After releasing the mold, the flowability was recorded as the
diameter of the sample at specified times, and the working time was
determined as the time when the sample stops flowing back and
leaves a distinct line in the sample by slicing the sample with a
metal spatula outward from center toward the edge of the
sample.
The test data is summarized in Table 12. The epoxy modified cement
composition offers long working time, good smooth surface
appearance and excellent compressive strength.
TABLE-US-00009 TABLE 9 Composition of epoxy modified cement Binder
% 5.5% water:cement ratio 0.37 Filler:Binder 16.1:1 Part A Epon
828/Epodil 748 emulsion 5.65 Part B CA1 3.1 Airase 4500 0.05 Water
8.05 Part C White Portland Cement 31 Berkely #1 dry (from US
Silica) 51.1 Melflux 2651 0.16 Calcium sulfoaluminate 0.66 Total
100
TABLE-US-00010 TABLE 10 Composition of Part A: Epon 828/Epodil 748
emulsion Epon 828 50.4 Triton X405 2.5 Epodil 748 11.1 DI Water 36
Total 100
TABLE-US-00011 TABLE 11 Composition of polyurethane modified cement
Part A FasTop 12S-Urethane Slurry GP4080 11.4% Part B FasTop
12S-Urethane Slurry GP4080 Hardener 11.4% Part C GP508CLC-50 5080
Light Gray 77.2%
TABLE-US-00012 TABLE 12 Test data summary of epoxy modified cement
and urethane modified cement Patent Comparison example: example:
Epoxy urethane modified modified Properties cement cement Working
time (minutes) 76 8 Flowability at 30 seconds (inches) 8.00 7.250
Flowability at 1 minute (inches) 8.25 7.375 Flowability at 5
minutes (inches) 8.50 7.750 Flowability at 10 minutes (inches) 8.50
8.000 Flowability at 30 minuntes (inches) 8.50 8.125 Compressive
strength at 7 days (psi) 6,942 4,757 Compressive strength at 28
days (psi) 8,164 4,706 Shore D Hardness 1 day 75 76 4 day 82 75 7
day 82 78 Surface evaluation Smooth, no Many bubbles/
bubbles/pinholes pinholes
* * * * *